Phase change ink formulation containing a combination of a urethane resin, a mixed urethane/urearesin, a mono-amide and a polyethylene wax

ABSTRACT

Phase change ink carrier compositions comprising an admixture of (1) at least one urethane resin; and/or (2) at least one mixed urethane/urea resin; and/or (3) at least one mono-amide; and/or (4) at least one polyethylene wax are provided. In addition, a phase change colored ink of such carrier compositions comprising a phase change ink compatible colorant are also provided. Embodiments of the present invention also include methods for producing a layer of the above phase change colored ink on the surface of a substrate by either direct or indirect printing. Such methods also encompassing using a polyethylene wax as an overcoat layer above such a phase change ink layer on a printed substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part application, which isa continuation-in-part of U.S. patent application Ser. No. 09/013,410,filed Jan. 26, 1998; which is a continuation-in-part application of U.S.patent application Ser. No. 08/672,815 filed on Jun. 28, 1996, now U.S.Pat. No. 5,830,942. This application is also a continuation in part ofU.S. patent application Ser. No. 09/078,190, filed May 13, 1998, whichis a continuation-in-part application of U.S. patent application Ser.No. 08/672,816 filed on Jun. 28, 1996.

BACKGROUND

[0002] 1. Field of the Invention

[0003] The present invention relates generally to phase change inks.Still further, the present invention relates to processes of using phasechange inks in printing devices. Additionally, the present inventionrelates to processes of using polyethylene wax as a transparent overcoatlayer on a printed substrate to provide improved document feedcapability from photocopiers.

[0004] 2. Description of the Relevant Art

[0005] In general, phase change inks (sometimes referred to as “hot meltinks”) are in the solid phase at ambient temperature, but exist in theliquid phase at the elevated operating temperature of an ink jetprinting device. At the jet operating temperature, droplets of liquidink are ejected from the printing device and, when the ink dropletscontact the surface of the printing media, they quickly solidify to forma predetermined pattern of solidified ink drops. Phase change inks havealso been investigated for use in other printing technologies such asgravure printing as referenced in U.S. Pat. No. 5,496,879 and Germanpatent publications DE 4205636AL and DE 4205713AL assigned to SiegwerkFarbenfabrik Keller, Dr. Rung and Co.

[0006] Phase change inks for color printing generally comprise a phasechange ink carrier composition, which is combined with a phase changeink compatible colorant. Preferably, a colored phase change ink will beformed by combining the above-described ink carrier composition withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black. U.S. Pat. Nos. 4,889,506; 4,889,761;and 5,372,852 teach that the subtractive primary colorants employedtypically may comprise dyes from the classes of Color Index (C.I.)Solvent Dyes, Disperse Dyes, modified Acid and Direct Dyes, and alimited number of Basic Dyes. The colorants can also include pigments asexemplified in U.S. Pat. No. 5,221,335, assigned to CoatesElectrographics LTD. U.S. patent application Ser. No. 08/381,610, filedJan. 30, 1995, and assigned to Tektronix, Inc. (now U.S. Pat. No.5,621,022), is directed to the use of a specific class of polymeric dyesin phase change ink compositions.

[0007] Phase change inks are desirable for ink jet printers since theyremain in a solid phase at room temperature during shipping, long-termstorage, and the like. Also, the problems associated with nozzleclogging due to ink evaporation are largely eliminated, therebyimproving the reliability of ink jet printing. Furthermore, ink dropletscan be applied directly onto a printing medium (substrate) and beconfigured to solidify immediately upon contact with the substrate.Migration of ink along the printing medium can thus be prevented and dotquality improved.

[0008] In addition to the above-referenced U.S. patents, many otherpatents describe materials for use in phase change ink jet inks. Somerepresentative examples include U.S. Pat. Nos. 3,653,932; 4,390,369;4,484,948; 4,684,956; 4,851,045; 4,889,560; 5,006,170; and 5,151,120; aswell as EP Application Nos. 0187352 and 0206286. These materials caninclude paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide-containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters are an example) andmany synthetic resins, oligomers, polymers and co-polymers.

[0009] Separately, PCT Patent Application WO 94/14902, which waspublished on Jul. 7, 1994 and is assigned to Coates Brothers PLC,teaches a hot melt ink containing a colorant and, as a vehicle for thehot melt ink, an oligourethane having a melting point of at least 65° C.and obtained by reacting an aliphatic or aromatic diisocyanate with atleast a stoichiometric amount of either: (i) a monohydric alcoholcomponent; or (ii) a monohydric alcohol component followed by anotherdifferent monohydric alcohol component; or (iii) a monohydric alcoholcomponent, followed by a dihydric alcohol component, followed by amonohydric alcohol component.

[0010] This PCT patent application defines the monohydric alcoholcomponent as either a monohydric aliphatic alcohol (e.g. C₁ to C₂₂alcohols), an etherified dihydric aliphatic alcohol (e.g. propyleneglycol methyl ether (PGME), dipropylene glycol methyl ether (DPGME),ethylene glycol butyl ether (EGBE), diethylene glycol butyl ether(DPGBE), tripropylene glycol butyl ether (TPGBE) and propylene glycolphenyl ether (PPL)); esterified dihydric aliphatic alcohol (e.g. theesterifying acid may be an ethylenically unsaturated acid (such asacrylic acid or methacrylic acid), thereby introducing ethylenicunsaturation into the oligourethane and rendering it suitable foreventual further additional polymerization (curing) after having beenapplied to a substrate by hot melt printing), or dihydric polyalkyleneglycol. This PCT Application further defines the dihydric alcoholcomponent as a dihydric aliphatic alcohol or a dihydric polyalkyleneglycol (e.g. ethylene glycol, polyethylene glycol (PEG 1500),polypropylene glycol (PPG 750, 1000 and 1500), trimethylene glycol,dipropylene glycol, methylpropanediol and 1,6-hexanediol).

[0011] Also, PCT Patent Application WO 94/04619, assigned to the GeneralElectric Company, teaches the use of ionomeric materials in combinationwith image forming agents to form a hot melt ink jet ink. The ionomericmaterials can include many different types of copolymeric or polymericionomers, including carboxyl-functional polyurethanes prepared from adiol or polyol and a hydroxyl acid. Many other carrier materials andcolorants for the image formiing agent of the invention are included inthis PCT application.

[0012] Furthermore, U.S. patent application Ser. No. 08/672,815, (nowU.S. Pat. No. 5,830,815) assigned to the Assignee of the presentinvention, teaches phase change carrier compositions that comprise thecombination of a urethane resin with a urethane/urea resin that mayoptionally contain other ingredients such as mono-amides andpolyethylene waxes.

[0013] However, there is still a need for new materials for novel anddifferent applications of phase change carrier compositions and inkscontaining such carrier compositions. There is a also a need for lowviscosity phase change carrier compositions and inks havingnon-polymeric resins and waxes designed for phase change ink jet andother forms of phase change ink printing. Such carrier compositions andinks being substantially transparent and having a reduced surfacecoefficient of friction as compared to presently known carriercompositions and inks. It would be advantageous if ink sticks which havean improved surface appearance and better release from molds and wastecollection trays than previously known ink sticks could also be formedfrom such carrier compositions and inks. Additionally, it would bedesirable if such phase change ink and carrier compositions includeimproved blocking performance offinished prints than has been previouslyknown.

BRIEF DESCRIPTION OF THE FIGURE

[0014] The FIGURE is a schematic diagram of a chemical reaction utilizedin particular aspects of the present invention.

SUMMARY

[0015] Embodiments in accordance with the present invention are directedto phase change carrier compositions comprising an admixture of (1) atleast one urethane resin; and/or (2) at least one mixed urethane/urearesin; and/or (3) at least one mono-amide; and/or (4) at least onepolyethylene wax.

[0016] Embodiments of the present invention are also directed to phasechange ink compositions comprising the admixture of (a) the above-notedphase change carrier composition with (b) a phase change ink compatiblecolorant.

[0017] Embodiments of the present invention include methods forproducing a layer of a phase change colored ink on the surface of asubstrate by either direct or indirect printing wherein the phase changeink composition in the solid phase comprises an admixture of (a) theabove-noted phase change carrier composition and (b) a phase change inkcompatible colorant.

[0018] Other embodiments in accordance with the present inventionencompass methods for using a polyethylene wax as an overcoat layerabove a phase change ink layer on a printed substrate such as a sheet ofpaper.

[0019] Features of embodiments of the present invention directed tophase change carrier compositions, include a low viscosity, beingsubstantially transparent and having a reduced surface coefficient offriction.

[0020] Features of embodiments in accordance with the present inventiondirected to phase change inks include ink sticks which have an improvedsurface appearance and better release from molds and waste collectiontrays than previously known ink sticks. Additional features of suchphase change ink embodiments also include improved blocking performanceof finished prints than has been previously known.

[0021] Advantageously, embodiments in accordance with the presentinvention encompassing phase change carrier compositions can be designengineered to obtain desired properties for specific printing platformsand architectures.

[0022] In addition, embodiments of the present invention that includephase change inks are resins or waxes which are very pure and that areessentially free of salts and other insoluble contaminants generallyfound in previously known phase change inks.

DETAILED DESCRIPTION

[0023] The term “nucleophile” in the present specification and claims isused as defined on page 179 of “Advanced Organic Chemistry”, 3rd Editionby Jerry March, 81985 by John Wiley and Sons, to describe a reagent thatbrings an electron pair to a reaction to form a new bond. The preferrednucleophiles of this invention are alcohols or amines, but it isunderstood that other nucleophilic functional groups that are capable ofreacting with the isocyanate moiety could also be used in the invention.

[0024] The term “oligomer” in the current specification and claims isused as defined on page 7 of “Polymer Chemistry—The Basic Concepts” byPaul Hiemenz, 81984 by Marcel Dekker, Inc., to describe a term coined todesignate molecules for which n (representing the number of repeatingmonomer units) is less than 10.

[0025] The term “isocyanate-derived resin” as used in the presentspecification and claims is defined as any monomeric, oligomeric ornon-polymeric resinous material derived from the reaction of mono-, di-,or poly-isocyanates with suitable nucleophilic molecules.

[0026] The terms “isocyanate-derived wax” as used in the presentspecification and claims is defined as any crystalline orsemicrystalline waxy material derived from the reaction of a fattyisocyanate with a suitable-nucleophile, or the reaction of a fattynucleophile with a suitable isocyanate, or the reaction of a fattynucleophile with a fatty isocyanate.

[0027] The term “urethane resin” or “urethane isocyanate-derived resin”as used in the present specification and claims is defined as any resinthat is a urethane which is the product of the reaction of an isocyanateand an alcohol.

[0028] The term “mixed urethane/urea resin” or “urethane/ureaisocyanate-derived resin” as used in the present specification andclaims is defined as any resin that is a mixed urethane/urea which isthe product of the reaction of an isocyanate, an alcohol and an amine.

[0029] Any suitable reaction condition for making urethane resins ormixed urethane/urea resins by condensing alcohols and/or amines withisocyanates can be employed in the practice of the present invention.Generally, the reaction is carried out at elevated temperatures (e.g.about 60° C. to about 160° C.) in the presence of a urethane reactioncatalyst such as dibutyltindilaurate, bismuth tris-neodecanoate, cobaltbenzoate, lithium acetate, stannous octoate or triethylamine. Thereaction conditions are typically an inert atmosphere, such as argon ornitrogen gas or other suitable atmosphere, to prevent oxidizing oryellowing the reaction products and to prevent undesirable sidereactions. The mole ratio of reactants is adjusted so that theisocyanate functionalities are completely consumed in the reaction witha slight molar excess of alcohol or amine typically remaining.Conceptually the reactants can be added together in any order and/oradded to the reaction as physical mixtures. However, in some embodimentsin accordance with the present invention, reaction conditions and theorder of the addition of reactants are controlled. First, reactionconditions and reactant additions are selected to provide a controlledexothermic reaction. Secondly, when reacting mixtures of alcohols and/oramines with diisocyanates such as isophorone diisocyanate (IPDI), theorder of addition of the isocyanate and the different nucleophiles tothe reaction is chosen to tailor the distribution of diurethanemolecules, and/or mixed urethane/urea molecules, and/or diurea moleculesin the final resin. When doing this, the different reactivities toisocyanates of alcohols versus amines are employed, as are the differentreactivities of the two separate isocyanate groups on IPDI. See J. H.Saunders and K. C. Frisch's “Polyurethanes Part I, Chemistry” publishedby Interscience of New York, N.Y. in 1962 and Olin Chemicals' Luxate™ IMisophorone diisocyanate technical product information sheet whichprovide further explanation of this chemistry. This control of thereaction conditions and order of addition of the reactants is done tospecifically tailor or customize the different types of molecularspecies in the finished resin so that the resin will:

[0030] (1) have a controlled viscosity that is designed for a specificapplication,

[0031] (2) have a controlled glass transition temperature and/or meltingpoint, and

[0032] (3) have consistent properties from batch to batch.

[0033] The isocyanate-derived resins from these reactions are generallytransparent solids having melting points in the range of about 20° C. toabout 150° C., viscosities in the range of about 10 cPs to about 5000cPs at 150° C. and T_(g)'s (glass transition point) of about −30° C. toabout 100° C. The isocyanate-derived waxes from these reactions aregenerally opaque waxy solids having sharp melting points from about 50°C. to about 130° C., and viscosities of about 1 cPs to about 25 cPs at140° C. Such resins and waxes display properties such that the higherthe T_(g) and the melting point, the higher the viscosity. While thestructural activity relationships are not fully understood, it is knownthat the T_(g) of isocyanate-derived resins is controlled by the properchoice of the mixture of nucleophiles in the reaction as illustrated inTable 3 in the aforementioned U.S. application Ser. No. 08/672,815 (nowU.S. Pat. No. 5,830,942). Varying one or more of the readily availablecommodity chemicals used as chemical precursors will permitcustom-tailoring of the properties of the isocyanate-derived resin andwax materials.

[0034] Alcohols employed in some embodiments of the present invention toreact with difunctional and higher isocyanates to make either theurethane resins or the urethane/urea resins of this invention includemonohydric alcohols. For instance, such monohydric alcohol encompass anyaliphatic alcohol [e.g., a C₁-C₂₂ or higher linear alcohol, any branchedalcohol or any cyclic aliphatic alcohol such as methanol, ethanol, (n-and iso)-propanol, (n-, iso-, t-) butanol, (n-, iso-, t-, and the like)pentanol, (n-, iso-, t-, and the like) hexanol, (n-, iso-, t-, and thelike) octanol, (n-, iso-, t-, and the like) nonanol, (n- and branched)decanols, (n- and branched) undecanols, (n- and branched) dodecanols,(n- and branched) hexadecanols, (n- and branched) octadecanols,3-cyclohexyl-1-propanol, 2-cyclohexyl-1-ethanol, cyclohexylmethanol,cyclohexanol, 4-methyl cyclohexanol, 4-ethylcyclohexanol,4-t-butylcyclohexanol, and the like]; an aliphatic/aromatic alcohol[e.g., benzyl alcohol, octyl, nonyl, and dodecylphenol alkoxylates ofoctyl, nonyl, and dodecylphenol, and alkoxyphenol]; aromatic alcoholssuch as phenol, naphthol, and the like, and their derivatives; fusedring alcohols (e.g., rosin alcohols, hydroabietyl alcohol, cholesterol,vitamin E, and the like). In some embodiments of the present invention,other alcohols are employed and include N,N-dimethyl-N-ethanolamine,stearamide-monoethanolamine, tripropyleneglycol monomethylether,hydroxybutanone, menthol, isoborneol, terpineol, 12-hydroxy stearylstearamide, and the like. In some embodiments, small amounts (on a molarbasis) of polyols are incorporated into the reaction mixture to produceoligomeric species in the resins. Such polyols include, hydroabietylalcohol, octylphenol ethoxylate and octadecyl alcohol.

[0035] Embodiments in accordance with the present invention employamines to react with difunctional and higher isocyanates to make mixedurethane/urea resins. Such amines include any monofunctional amine, withthe exception of any tertiary amine void of another nucleophilicfunctional group (e.g., triethylamine). Thus, mono-amines of someembodiments of the present invention encompass aliphatic primary orsecondary amines (e.g., a C₁-C₂₂ or higher linear amine, any branchedamine or any cyclic aliphatic amine) such as methyl amine, ethyl amine,(n- and iso-)propyl amine, (n-, iso-, and t-) butyl amine, (n-, iso-,t-, and the like) pentyl amine, (n-, iso-, t-, and the like) hexylamine, (n-, iso-, t-, and the like) octyl amine, (n-, iso-, t-, and thelike) nonyl amine, (n- and branched) decyl amine, (n- and branched)undecyl amines, (n- and branched) dodecyl amines, (n- and branched)hexadecyl amines, (n- and branched) dodecyl amines, dimethyl amine,diethyl amine, di(n- and iso-)propyl amines, di(n-, iso-, t-)butylamine, di(n-, iso-, t-, and the like)pentyl amine, di(n-, iso-, t-, andthe like)hexyl amine, di(n-, iso-, t-, and the like)cyclohexyl amine,di(n-, iso-, t-, and the like)heptyl amine, di(n-, iso-, t-, and thelike)octyl amine, di(n-, iso-, t-, and the like)decyl amine, di(n-,iso-, t-, and the like)dodecyl amine, di(n-, iso-, t-, and thelike)octadecyl amine, cyclohexyl amine, 2,3-dimethyl-1-cyclohexylamine,piperidine, pyrrolidine, and the like. Such mono-amines also encompassaliphatic/aromatic amines (e.g., benzyl amine or analogues with longeror additional alkyl chains); aromatic amines such as aniline, anisidine,and the like; fused ring amines such as rosin amine, dehydroabietylamine, dihydroabietyl amine, hydroabietyl amine, and the like; andmiscellaneous amines (e.g., adamantyl amine, isonipecotamide,polyoxyalkylenemonoamines, such as M-series Jeffamines availablecommercially from Huntsman Chemical Company of Austin, Tex.).;3,3′-diamino-N-methyl-dipropylamine, and the like. In addition, inembodiments where oligeomeric species are formed, small amounts (on amolar basis) of polyamines are incorporated into the reaction mixture. Asuitable amine is octadecyl amine.

[0036] Alcohols for reacting with monofunctional isocyanates to make themixed urethane/urea resins in accordance with some embodiments of thisinvention include any monohydric alcohol. For instance, such monohydricalcohols are any aliphatic alcohol [e.g., a C₁-C₂₂ or higher linearalcohol, any branched alcohol or any cyclic aliphatic alcohol such asmethanol, ethanol, (n- and iso-)propanol, (n-, iso-, and t-) butanol,(n-, iso-, t-, and the like) pentanol, (n-, iso-, t-, and the like)hexanol, (n-, iso-, t-, and the like) octanol, (n-, iso-, t-, and thelike) nonanol, (n- and branched) decanols, (n- and branched) undecanols,(n- and branched) dodecanols, (n- and branched) hexadecanols, (n- andbranched) octadecanols, 3-cyclohexyl-1-propanol, 2-cyclohexyl-1-ethanol,cyclohexylmethanol, cyclohexanol, 4-methyl cyclohexanol,4-ethylcyclohexanol, 4-t-butylcyclohexanol, and the like]; analiphatic/aromatic alcohol (e.g., benzyl alcohol, octyl, nonyl, anddodecylphenol alkoxylates or octyl, nonyl, and dodecylphenol,alkoxyphenol); aromatic alcohols such as phenol, naphthol, and the like,and their derivatives; fused ring alcohols (e.g., rosin alcohols,hydroabietyl alcohol, cholesterol, vitamin E, and the like). Othersuitable alcohols include N,N-dimethyl-N-ethanolamine,stearamide-monoethanolamine, tripropyleneglycol monomethylether,hydroxybutanone, menthol, isoborneol, terpineol, 12-hydroxy stearylstearamide, and the like. Further, multifunctional alcohols can beutilized in some embodiments of the present invention. Exemplarymultifunctional alcohols are ethylene glycol, diethylene glycol,triethylene glycol, dimethylolpropionic acid, sucrose,polytetramethylene glycol (MW<-3000), polypropylene glycol (MW<-3000),polyester polyols (MW<-3000), polyethylene glycol (MW<-3000),pentaerythritol, triethanol amine, glycerin, 1,6-hexanediol,N-methyl-N,N-diethanol amine, trimethylol propane,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, and the like. Insome embodiments in accordance with the present invention, octadecanolis employed.

[0037] Some embodiments of the present invention encompass amines forreacting with monofunctional isocyanates to make isocyanate-derivedwaxes and resins. Such amines include monofunctional amines, with theexception of tertiary amines void of another nucleophilic functionalgroups (e.g., triethylamine). For instance, the monoamine could be anyaliphatic primary or secondary amine [e.g., a C₁-C₂₂ or higher linearamine, any branched amine or any cyclic aliphatic amine such as methylamine, ethyl amine, (n- and iso-)propyl amine, (n-, iso-, and t-) butylamine, (n-, iso-, t-, and the like) pentyl amine, (n-, iso-, t-, and thelike) hexyl amine, (n-, iso-, t-, and the like) octyl amine, (n-, iso-,t-, and the like) nonyl amine, (n- and branched) decyl amine, (n- andbranched) undecyl amine, (n- and branched) octadecyl amine, (n- andbranched) hexadecyl amine, (n- and branched) dodecyl amine, dimethylamine, diethyl amine, di(n-, and iso-)propyl amine, di(n-, iso-,t-)butyl amine, di(n-, iso-, t-, and the like)pentyl amine, di(n-, iso-,t-, and the like)hexyl amine, di(n-, iso-, t-, and the like)cyclohexylamine, di(n-, iso-, t-, and the like)heptyl amine, di(n-, iso-, t-, andthe like)octyl amine, di(n-, iso-, t-, and the like)decyl amine, di(n-,iso-, t-, and the like)octadecyl amine, di(n-, iso-, t-, and thelike)dodecyl amine, cyclohexyl amine, 2,3-dimethyl-1-cyclohexylamine,piperidine, pyrrolidine, and the like]; any aliphatic/aromatic amines(e.g., benzyl amine or analogues with longer or additional alkylchains); aromatic amines such as aniline, anisidine, and the like; fusedring amines such as rosin amine, dehydroabietyl amine, dihydroabietylamine, hydroabietyl amine, and the like. Also, miscellaneous amines(e.g., adamantyl amine, isonipecotamide, polyoxyalkylenemono-, di-, ortriamines, such as M-, D-, and T-series Jeffamines availablecommercially from Huntsman Chemical Company of Austin, Tex.);3,3′-diamino-N-methyl-dipropylamine, and the like can be utilized, aswell as multifunctional amines such as polyethylene imine; ethylenediamine; hexamethylene diamine; isomers of cyclohexyldiamines;1,3-pentadiamine; 1,12-dodecanediamine; 3-dimethylamino-propylamine;4,7,10-trioxa-1,13-tridecanediamine; diethylene triamine;3,3-diamino-N-methyldipropylamine; tris(2-aminoethyl)amine, and thelike. A preferred amine can be octadecylamine.

[0038] Additionally, hydroxyl/amino containing compounds can be employed(with di- and higher functionality isocyanates taking advantage of thedifference in reactivity of the amine over the hydroxyl group, or withmonoisocyanates reacting with the amine preferentially or with both theamine and the hydroxyl groups). Examples of this include ethanolamine,diethanolamine, and the like.

[0039] Additionally, amides or other nucleophile containing compoundscan be reacted with the isocyanates (mono, di, and the like). Someexamples include: urea, oleamide, stearamide, or the like.

[0040] Preferred precursors to the urethane resins and urethane/urearesins of the present invention include mono-, di- and otherpoly-isocyanates. Examples of monoisocyanates includeoctadecylisocyanate; octylisocyanate; butyl and t-butylisocyanate;cyclohexyl isocyanate; adamantyl isocyanate; ethylisocyanatoacetate;ethoxycarbonylisocyanate; phenyliso-cyanate; alphamethylbenzylisocyanate; 2-phenylcyclopropyl isocyanate; benzylisocyanate;2-ethylphenylisocyanate; benzoylisocyanate; meta andpara-tolylisocyanate; 2-, 3-, or 4-nitrophenylisocyanates;2-ethoxyphenyl isocyanate; 3-methoxyphenyl isocyanate;4-methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate;2,6-dimethylpherylisocyante; 1-naphthylisocyanate;(naphthyl)ethylisocyantes; and the like. Examples of diisocyanatesinclude isophorone diisocyanate (IPDI); toluene diisocyanate (TDI);diphenylmethane-4,4′-diisocyanate (MDI); hydrogenateddiphenylmethane-4,4′-diisocyanate (HDI); tetra-methyl xylenediisocyanate (TMXDI); hexamethylene-1,6-diisocyanate (HDI);hexamethylene-1,6-diisocyanate; napthylene-1,5-diisocyanate;3,3′-dimethoxy-4,4′-biphenyldiisocyanate;3,3′-dimethyl-4,4′-bimethyl-4,4′-biphenyldiisocyanate; phenylenediisocyanate; 4,4′-biphenyldiisocyanate; trimethylhexamethylenediisocyanate; tetramethylene xylene diisocyanate;4,4′-methylenebis(2,6-diethylphenyl isocyanate);1,12-diisocyanatododecane; 1,5-diisocyanato-2-methylpentane;1,4-diisocyanatobutane; and cyclohexylene diisocyanate and its isomers;uretidione dimers of HDI; and the like. Examples of triisocyanates ortheir equivalents include the trimethylolpropane trimer of TDI, and thelike, isocyanurate trimers of TDI, HDI, IPDI, and the like, and biurettrimers of TDI, HDI, IPDI, and the like. Examples of higher isocyanatefunctionalities include copolymers of TDI, HDI, and the like, as well asMI oligomers.

[0041] Phase change inks of this invention can contain a phase changecarrier system or composition. The phase change carrier composition isgenerally designed for use in either a direct printing mode or use in anindirect or offset printing transfer system. In the direct printingmode, the phase change carrier composition is generally made up of oneor more chemicals that provide properties to allow the phase change ink(1) to be applied in a thin film of uniform thickness on the finalreceiving substrate when cooled to the ambient temperature afterprinting directly to the substrate; (2) to be ductile while retainingsufficient flexibility so that the applied image on the substrate willnot fracture upon bending; and (3) to possess a high degree oflightness, chroma, transparency and thermal stability. In an offsetprinting transfer or indirect printing mode, the phase change carriercomposition is designed to possess not only the above mentionedproperties, but certain fluidic and mechanical properties, as describedin U.S. Pat. No. 5,389,958. Exemplary phase change carrier compositionand the inks made therefrom comprised by the current invention containurethane resins, or urethane/urea resins. The carrier compositions canbe supplemented with (one or more) additional ingredients to preparecommercial phase change carrier compositions. The urethane resins, andmixed urethane/urea resin materials of the current invention can betailored to have the desirable properties mentioned above when used inthe carrier composition of the inks of the present invention by varyingone or more of the readily available commodity chemical precursors.

[0042] The phase change carrier compositions of the current inventionmay be used in combination with conventional phase change ink colorantmaterials such as Color Index (C.I.) Solvent Dyes, Disperse Dyes,modified Acid and Direct Dyes, Basic Dyes, Sulphur Dyes, Vat Dyes,and/or polymeric dyes such as those disclosed in U.S. patent applicationSer. No. 08/381,610 (now U.S. Pat. No. 5,621,022), and/or pigments toproduce a phase change ink. Alternatively, the phase change carriercompositions of the current invention may employ colored urethane resinsor urethane/urea resins or other isocyanate-derived colored resins asdescribed in U.S. patent application Ser. No. 08/672,617, filed Jun. 28,1996 and assigned to the assignee of the present invention (now U.S.Pat. No. 5,780,528), to produce a phase change ink.

[0043] Phase change carrier compositions of the present invention cancomprise a mono-amide. A mono-amide compound typically comprises eithera primary or secondary mono-amide, but is preferably a secondarymono-amide. Of the primary mono-amides, stearamide, such as KEMAMIDE S,manufactured by Witco Chemical Company, can be employed herein. As forthe secondary mono-amides, behenyl benenamide (KEMAMIDE EX-666), andstearyl stearamide (KEMAMIDE S-180), both manufactured by Witco ChemicalCompany, are extremely useful mono-amides. However, stearyl stearamide(KEMAMIDE S-180) is the mono-amide of choice in producing the phasechange ink compositions of the present invention.

[0044] Phase change carrier compositions of the present invention cancomprise at least one polyethylene wax. Preferably, the polyethylene waxhas a molecular weight of about 500 to about 5,000; more preferably, ofabout 550 to about 2,000; and, most preferably, of about 500 to 1,000.Suitable polyethylene waxes are Polywax 655, Polywax 850, or Polywax1000, all available from Petrolite.

[0045] Preferably, the total amount of urethane resin or resins in thephase change carrier composition and the inks made therefrom willcomprise about 10% to about 40%, more preferably, about 15-35% and mostpreferably, about 20-30%, by weight of the carrier composition.Preferably, the total amount of mixed urethane/urea resin or resins inthe phase change carrier composition will likewise comprise about 10% toabout 40%, more preferably about 15-35% and most preferably, about20-30%, by weight of the carrier composition. Preferably, the totalamount of mono-amide wax and polyethylene wax combined will compriseabout 40% to about 70%, more preferably, about 45-60% and mostpreferably about 48-57% by weight of the carrier composition.

[0046] The ratio of mono-amide wax to the polyethylene wax is preferablyfrom about 200:1 to 9:1, by weight. More preferably, this ratio is fromabout 50:1 to about 12:1, by weight and, most preferably, about 25:1 toabout 16:1, by weight.

[0047] Prior art phase change inks for use in direct and indirecttransfer printing systems are described in U.S. Pat. Nos. 4,889,560 and5,372,852. These inks consist of a phase change ink carrier compositioncomprising one or more fatty amide-containing materials, usuallyconsisting of a mono-amide wax and a tetra-amide resin, one or moretackifiers, one or more plasticizers and one or more antioxidants, incombination with compatible colorants. A preferred tetra-amide resin isa dimer acid based tetra-amide that is the reaction product of dimeracid, ethylene diamine, and stearic acid. The typical mono-amide isstearyl stearamide. A preferred tackifier resin is a glycerol ester ofhydrogenated abietic (rosin) acid and a preferred antioxidant is thatprovided by Uniroyal Chemical Company under the tradename Naugard 524.The urethane and urethane/urea resins employed in this invention canreplace one or more of the ingredients in this prior art carriercomposition or inks employing the resin components of the presentinvention can have all of these prior art ingredients replaced by theurethane and/or urethane/urea resins disclosed herein and/or byisocyanated derived waxes.

[0048] Among the advantages of inks formulated in accordance with thepresent invention relative to prior art phase change inks are:

[0049] (1) The urethane resins and mixed urethane/urea resins of thisinvention are very pure, being free of salts and other insolublecontaminants. This makes the inks made from these materials easy tofilter and provides for high reliability in ink jet printing devices.This can be a major advantage.

[0050] (2) The urethane resins and mixed urethane/urea resins of thisinvention may be specifically tailored to give certain physicalproperties that optimize the performance of the inks of this inventionin ink jet printing devices and on the output substrate. These desirableink properties include melting point, viscosity, transparency and thedynamic mechanical properties referenced in the aforementioned U.S. Pat.No. 5,389,958.

[0051] (3) The urethane resins and mixed urethane/urea resins of thisinvention are used in combination with the mono-amide wax andpolyethylene wax to give ink compositions that display an improved yieldstress versus temperature curve over prior art ink compositions. Thisenables ink droplets to be spread and fused at elevated temperaturesduring the fusing and transfer steps in an indirect printing process,but at a lower pressure than was possible with prior art inks.

[0052] (4) The ink formulations with the added polyethylene waxdisclosed herein exhibit better surface finishes in the final poured,molded and hardened ink sticks when compared to equivalent ink sticksformulated without the polyethylene wax, as well as exhibiting betterrelease characteristics from their plastic molds. The waste inkresulting from ink sticks of the present invention also releases moreeasily from the waste ink trays in the printers for which they areintended for use. Finally, prints made from inks with the polyethylenewax additive also exhibit better blocking resistance at elevatedtemperatures.

[0053] Many other patents describe other materials for use in phasechange ink jet inks. Some representative examples include U.S. Pat. Nos.3,653,932; 4,390,369; 4,484,948; 4,684,956; 4,851,045; 5,006,170;5,151,120; EP Application Nos. 0187352 and 0206286; and PCT PatentApplication WO 94/04619. These other materials can include paraffins,microcrystalline waxes, ester waxes, amide waxes, fatty acids, fattyalcohols, fatty amides and other waxy materials, sulfonamide materials,resinous materials made from different natural sources (tall oil rosinsand rosin esters are an example) and many synthetic resins, oligomers,polymers, co-polymers, and ionomers. It will be obvious to those skilledin the art that the phase change carrier composition of this inventioncould optionally contain any of the optional other materials.

[0054] The aforementioned U.S. Pat. No. 5,496,879 and German patentpublications DE 4205636AL and DE 4205713AL, assigned to SiegwerkFarbenfabrik Keller, Dr. Rung and Co., describe materials used for phasechange or hot melt gravure printing. It will be obvious to those skilledin the art that the isocyanate-derived materials of this currentinvention would be compatible with those materials and could also beused in that application or other similar printing methods that employhot melt ink technology.

[0055] It also will be obvious to those skilled in the art that otherink colors besides the subtractive primary colors are desirable forapplications, such as postal marking or industrial marking and labelingusing phase change printing, and that this invention is applicable tothese needs. Infrared (IR) or ultraviolet (UV) absorbing dyes can alsobe incorporated into the inks of this invention for use in applicationssuch as “invisible” coding or marking of products.

[0056] The inks of the present invention can be equally well employed inapparatus for direct or indirect (offset) printing applications. Whenemployed in direct printing applications a suitable method of printingor producing a layer of a phase change colored ink directly on thesurface of a substrate can comprise:

[0057] (1) forming a phase change ink composition in the solid phase,comprising an admixture of (a) a phase change carrier compositioncontaining at least one isocyanate-derived resin or wax and (b) a phasechange compatible colorant.

[0058] (2) transferring the solid phase, phase change colored inkcomposition to a phase change ink application means or print head;

[0059] (3) raising the operating temperature of the application means orprint head to a level whereby a liquid phase, phase change colored inkcomposition is formed;

[0060] (4) providing a substrate in proximity to the application means;

[0061] (5) applying a predetermined pattern of the liquid phase, phasechange colored ink composition to at least one surface of the substrate;and

[0062] (6) lowering the temperature of the applied ink composition toform a solid phase, phase change ink pattern on the substrate.

[0063] An appropriate direct printing process is described in greaterdetail in U.S. Pat. No. 5,195,430.

[0064] When employed in indirect or offset printing applications asuitable method of printing or producing a layer of a phase changecolored ink indirectly on the surface of a substrate by transferringfrom an intermediate transfer surface can comprise:

[0065] (1) forming a phase change ink composition in the solid phase,comprising an admixture of (a) a phase change carrier compositioncontaining at least one isocyanate-derived resin or wax and (b) a phasechange compatible colorant.

[0066] (2) transferring the solid phase, phase change colored inkcomposition to a phase change ink application means or a print head;

[0067] (3) raising the operating temperature of the application means orprint head to a level whereby a liquid phase, phase change colored inkcomposition is formed;

[0068] (4) providing an intermediate transfer surface in proximity tothe application means;

[0069] (5) applying a predetermined pattern of the liquid phase, phasechange colored ink composition to the intermediate transfer surface;

[0070] (6) lowering the temperature of the applied ink composition toform a solid phase, phase change ink pattern on the intermediatetransfer surface at a second, intermediate temperature;

[0071] (7) transferring said phase change ink composition from theintermediate transfer surface to a final substrate; and

[0072] (8) fixing the phase change ink composition to the substrate toform a printed substrate, the phase change ink composition having (a) acompressive yield strength which will allow it to be malleable to spreadand deform without an increase in stress when compressive forces areapplied thereto at the second operating temperature, and sufficientinternal cohesive strength to avoid shear banding and weak behavior whensaid phase change ink composition is transferred and fixed to saidsubstrate, and (b) a ductility on the substrate after fixing.

[0073] An appropriate offset or indirect printing process is describedin greater detail in U.S. Pat. No. 5,389,958.

[0074] The polyethylene wax of this invention can also be employed as anovercoat layer on a printed substrate. In this application, a substrate,preferably paper, is printed with any ink, preferably with a phasechange ink, more preferably with a phase change ink composition of thepresent invention. The printed substrate is then coated with thepolyethylene wax described above. Preferably, this overcoat only coatsaminority portion of the surface area of the printed substrate, morepreferably a regularly spaced dot matrix covering from about 1% to about25% of the surface area of the printed substrate.

[0075] In one example of using an overcoat, printed pages of paper aremade on a Tektronix Phaser™ 340 ink jet ink printer by conventionalmeans. The thus-produced printed paper then has a matrix of polyethylenewax dots (with about a 1% to about 5% fill) printed over the image. Thiswax dot matrix can be printed with another or the same ink jet printer.Preferably, the substrate after this overcoat operation is passedthrough a set of pressure rollers in the same ink jet printer to embedthe polyethylene wax into the surface of the printed substrate. Thistreatment gives enhanced antiblocking properties to the prints (lesstransfer of ink from page to paper lying on top of output page whenweighted and left standing) and also enables the prints to be fedthrough a copier automatic document feed (ADF) because of the decreasedstickiness of the ink. Alternatively, the polyethylene wax could beapplied to finished prints by other means such as an anilox roller, orcould be jetted onto the transfix drum in an appropriate dot or othermatrix before the rest of the image is applied to that drum, thusleaving the dot matrix of wax on top of the image after the transfixprocess.

[0076] The present invention is further described in detail by means ofthe following Examples and Comparisons. All parts and percentages are byweight and all temperatures are degrees Celsius unless explicitly statedotherwise. It is to be noted that while the following examples mayrecite only one colorant, it is to be understood that each individualexample is only illustrative and any of the primary colorants (cyan,yellow, magenta and black) used in subtractive color printing could beemployed in each instance.

[0077] A particular embodiment of the present invention is describedwith reference to the FIGURE as a method of forming a urethane material.Specifically, ABITOL E™ (available form Hercules) is utilized as astarting reagent. ABITOL E is shown by a representative structure, andcomprises hydroabietyl alcohol (CAS[133-93-6]), methyl ester ofhydrogenated rosin (CAS[8050-15-5]), and decarboxylated rosin(CAS[8050-18-8])). The ABITOL E is reacted with isophorone diisocyanate(CAS[4098-71-91]) to form a urethane product. Typically,dibutyltindilaurate (CAS[77-58-7]) is provided as a catalyst (and isprovided to a concentration of less than 1% by weight relative to otherreactants). The relative amount of isophorone diisocyanate to ABITOL Eis preferably such that the isophorone diisocyanate is a limitingreagent in the reaction.

[0078] ABITOL E is an exemplary alcohol reagent. Such exemplary reagentis a member of a class of monohydric alcohols comprising fused rings.The fused rings may or may not comprise double bonds. The exemplaryreagent is also a member of a class of alcohols comprising at leastthree fused rings.

[0079] The urethane product is a member of a class of materials that canbe represented by formula 1.

[0080] The groups R₁—R₁₉ of formula 1 each comprise, independently ofthe others, a hydrogen atom, an alkyl group (either substituted orunsubstituted), which can be linear, branched, unsaturated, and/orcyclic, typically with from about 1 to about 100 carbon atoms,preferably with from about 12 to about 60 carbon atoms, and morepreferably with from about 18 to about 50 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, an aryl group(either substituted or unsubstituted), typically with from about 6 toabout 24 carbon atoms, preferably with from about 6 to about 14 carbonatoms, and more preferably with from about 6 to about 10 carbon atoms,although the number of carbon atoms can be outside of these ranges, anarylalkyl group or alkylaryl group (either substituted orunsubstituted), typically with from about 7 to about 100 carbon atoms,preferably with from about 10 to about 60 carbon atoms, and morepreferably with from about 18 to about 50 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, a heterocyclicgroup (either substituted or unsubstituted), typically with from about 3to about 50 carbon atoms, preferably with from about 3 to about 18carbon atoms, and more preferably with from about 3 to about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges, wherein the hetero atom or atoms can be, but are not limited to,atoms such as oxygen, nitrogen, sulfur, phosphorus, silicon, and thelike, as well as mixtures thereof, wherein two or more of the R groupscan be joined together to form a ring, and where the substituents on thesubstituted alkyl, aryl, arylalkyl, alkylaryl, and heterocyclic groupscan be (but are not limited to) hydroxy groups, amine groups, iminegroups, ammonium groups, pyridine groups, pyridinium groups, ethergroups, aldehyde groups, ketone groups, ester groups, amide groups,carboxylic acid groups, carbonyl groups, thiocarbonyl groups, sulfategroups, sulfonate groups, sulfide groups, sulfoxide groups, phosphinegroups, phosphonium groups, phosphate groups, cyano groups, nitrilegroups, mercapto groups, nitroso groups, halogen atoms, nitro groups,sulfone groups, acyl groups; acid anhydride groups, azide groups,mixtures thereof, and the like, wherein any two or more substituents canbe joined together to form a ring. Further one or more of groups R₁—R₁₉can be comprised by a ring structure. The segment (CH₂)_(x) comprisesone or more methylene groups.

[0081] A more specific description of a class encompassing the urethaneproduct of the FIGURE is shown below as formula 2.

[0082] The groups R₁—R₃₀ of formula 2 comprise, independently of theothers, a hydrogen atom, an alkyl group (either substituted orunsubstituted), which can be linear, branched, unsaturated, and/orcyclic, typically with from about 1 to about 100 carbon atoms,preferably with from about 12 to about 60 carbon atoms, and morepreferably with from about 18 to about 50 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, an aryl group(either substituted or unsubstituted), typically with from about 6 toabout 24 carbon atoms, preferably with from about 6 to about 14 carbonatoms, and more preferably with from about 6 to about 10 carbon atoms,although the number of carbon atoms can be outside of these ranges, anarylalkyl group or alkylaryl group (either substituted orunsubstituted), typically with from about 7 to about 100 carbon atoms,preferably with from about 10 to about 60 carbon atoms, and morepreferably with from about 18 to about 50 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, a heterocyclicgroup (either substituted or unsubstituted), typically with from about 3to about 50 carbon atoms, preferably with from about 3 to about 18carbon atoms, and more preferably with from about 3 to about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges, wherein the hetero atom or atoms can be, but are not limited to,atoms such as oxygen, nitrogen, sulfur, phosphorus, silicon, and thelike, as well as mixtures thereof, wherein two or more of the R groupscan be joined together to form a ring, and where the substituents on thesubstituted alkyl, aryl, arylalkyl, alkylaryl, and heterocyclic groupscan be (but are not limited to) hydroxy groups, amine groups, iminegroups, ammonium groups, pyridine groups, pyridinium groups, ethergroups, aldehyde groups, ketone groups, ester groups, amide groups,carboxylic acid groups, carbonyl groups, thiocarbonyl groups, sulfategroups, sulfonate groups, sulfide groups, sulfoxide groups, phosphinegroups, phosphonium groups, phosphate groups, cyano groups, nitrilegroups, mercapto groups, nitroso groups, halogen atoms, nitro groups,sulfone groups, acyl groups, acid anhydride groups, azide groups,mixtures thereof, and the like, wherein any two or more substituents canbejoined together to form a ring. The segments (CH₂)_(x), (CH₂)_(y), and(CH₂)_(z) comprise one or more methylene groups and can be the same asone another or different from one another.

[0083] A yet more specific description of a class encompassing theurethane product of the FIGURE is shown below as formula 3.

[0084] The groups R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ of formula 3comprise, independently of the others, a hydrogen atom, an alkyl group(either substituted or unsubstituted), which can be linear, branched,unsaturated, and/or cyclic, typically with from about 1 to about 100carbon atoms, preferably with from about 12 to about 60 carbon atoms,and more preferably with from about 18 to about 50 carbon atoms,although the number of carbon atoms can be outside of these ranges, anaryl group (either substituted or unsubstituted), typically with fromabout 6 to about 24 carbon atoms, preferably with from about 6 to about14 carbon atoms, and more preferably with from about 6 to about 10carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group or alkylaryl group (either substitutedor unsubstituted), typically with from about 7 to about 100 carbonatoms, preferably with from about 10 to about 60 carbon atoms, and morepreferably with from about 18 to about 50 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, a heterocyclicgroup (either substituted or unsubstituted), typically with from about 3to about 50 carbon atoms, preferably with from about 3 to about 18carbon atoms, and more preferably with from about 3 to about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges, wherein the hetero atom or atoms can be, but are not limited to,atoms such as oxygen, nitrogen, sulfur, phosphorus, silicon, and thelike, as well as mixtures thereof, wherein two or more of the R groupscan be joined together to form a ring, and where the substituents on thesubstituted alkyl, aryl, arylalkyl, alkylaryl, and heterocyclic groupscan be (but are not limited to) hydroxy groups, amine groups, iminegroups, ammonium groups, pyridine groups, pyridinium groups, ethergroups, aldehyde groups, ketone groups, ester groups, amide groups,carboxylic acid groups, carbonyl groups, thiocarbonyl groups, sulfategroups, sulfonate groups, sulfide groups, sulfoxide groups, phosphinegroups, phosphonium groups, phosphate groups, cyano groups, nitrilegroups, mercapto groups, nitroso groups, halogen atoms, nitro groups,sulfone groups, acyl groups, acid anhydride groups, azide groups,mixtures thereof, and the like, wherein any two or more substituents canbe joined together to form a ring hydrogen, alkyl groups or aryl groups.

[0085] The urethane product of the FIGURE (or any members of theurethane products encompassed by formulas 1-3), can be incorporated intophase change inks. For instance, such urethane products can be combinedwith polyethylene waxes and/or mono-amide compounds to form phase changeink carrier compositions. Phase change inks comprising the urethaneproducts can be printed by, for example, either the direct or offsetprinting methodologies described previously.

EXAMPLE 1 The Reaction Product of Octyphenol Ethoxylate, IsophoroneDiisocyanate and Yellow Reactive Colorant

[0086] About 525.0 grams (4.73 equiv.) of isophorone diisocyanate¹ and1.5 grams of dibutyltindilaurate² catalyst, followed by 986 grams (3.88equiv.) of octylphenol ethoxylate³, were added to a 3000 ml three-neckresin kettle equipped with a Trubore stirrer, N₂ atmosphere inlet, and athermocouple-temperature controller. The reaction mixture was heated toabout 135° C., about 346.1 grams (0.497 equiv.) of a yellow polymericcolorant corresponding to Colorant A from Table I of U.S. Pat. No.5,231,135 were added and the reaction mixture was heated forapproximately 2 hours. An additional about 110.0 grams (0.433 equiv.) ofoctylphenol ethoxylate³ were added and the reaction mixture was heatedat about 150° C. for approximately 2 hours. An FT-IR of the product wasobtained to insure all of the isocyanate (NCO) functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethanefrequencies were used to confirm this. The diurethane reaction productwas poured into aluminum molds and allowed to cool and harden. Thisfinal colored resin product was characterized by the following physicalproperties: viscosity of about 121 cPs as measured by a Ferranti-Shirleycone-plate viscometer at about 140° C., a melting point of about 38° C.to about 115° C. as measured by electrothermal capillary melting pointapparatus, a T_(g) of about 12.4° C. as measured by differentialscanning calorimetry using a DuPont 2100 calorimeter at a scan rate of20° C./minute, and a spectral strength of about 5634 millilitersAbsorbance Units per gram at λ max as measured by dilution in n-butanolusing a Perkin Elmer Lambda 2S UV/VIS spectrophotometer.

EXAMPLE 2 The Reaction Product of 1.5 Parts Hydroabietyl Alcohol, 0.5Parts Octadecyl Amine, and Isophorone Diisocyanate

[0087] About 240.2 grams (0.676 moles) of hydroabietyl alcohol⁴ wasadded to a 1000 ml four-neck resin kettle equipped with a Truborestirrer, an N₂ atmosphere inlet, 200 ml addition funnel, and athermocouple temperature controller. About 100.0 grams (0.45 moles) ofisophorone diisocyanate⁵ was added to the addition funnel. Agitation ofthe hydroabietyl alcohol first was begun and then all of the isophoronediisocyanate was added over approximately 5 minutes. About 0.22 grams ofdibutyltindilaurate⁶ catalyst was added and the reaction mixture heatedto about 125° C. under anN₂ atmosphere. After4 hours at 125° C., about59.95 grams (0.225 moles) of octadecyl amine⁷ was added and thetemperature raised to about 150° C. and held for approximately 2 hours.An FT-IR of the reaction product was run to insure all of the NCOfunctionality was consumed. The absence (disappearance) of a peak atabout 2285 cm⁻¹ (NCO) and the appearance (or increase in magnitude) ofpeaks at about 1705-1635 cm⁻¹ and about 1515-1555 cm⁻¹ corresponding tourea frequencies and about 1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹corresponding to urethane frequencies were used to confirm this. Thefinal mixed urethane/urea resin product was poured into aluminum moldsand allowed to cool and harden. This final product was a clear solidresin at room temperature characterized by the following physicalproperties: viscosity of about 314.8 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C., a melting pointof from about 67.9° C. to about 87.0° C. as measured by anelectrothermal capillary melting point apparatus, and a T_(g) of about23° C. as measured by differential scanning calorimetry using a DuPont2100 calorimeter at a scan rate of 20° C./minute.

EXAMPLE 3 The Reaction Product of Octyphenol Ethoxylate, IsophoroneDiisocyanate and Cyan Reactive Colorant

[0088] About 525.0 grams (4.73 equiv.) of isophorone diisocyanate⁸,about 1.5 grams of dibutyltindilaurate⁹ catalyst, and about 992.0 grams(3.91 equiv.) of octylphenol ethoxylate¹⁰ were added to a 3000 mlthree-neck resin kettle equipped with a Trubore stirrer, a N₂ atmosphereinlet, and a thermocouple-temperature controller. The reaction mixturewas heated to about 135° C. and held for approximately 3.5 hours withstirring under nitrogen. About 240.6 grams (0.473 equiv.) of a cyanpolymeric colorant¹¹ were then added and the mixture was heated at about150° C. for approximately 2 hours. An FT-IR of the product was obtainedto insure all of the isocyanate (NCO) functionality was consumed. Theabsence (disappearance) of a peak at about 2285 cm⁻¹ (NCO) and theappearance (or increase in magnitude) of peaks at about 1740-1680 cm⁻¹and about 1540-1530 cm⁻¹ corresponding to urethane frequencies were usedto confirm this. The diurethane reaction product was poured intoaluminum molds and allowed to cool and harden. This final colored resinproduct was characterized by the following physical properties:viscosity of about 181.8 cPs as measured by a Ferranti-Shirleycone-plate viscometer at about 140° C., a melting point of about59.9-70.2° C. as measured by electrothermal capillary melting pointapparatus, and a T_(g) of about 23.1° C. as measured by differentialscanning calorimetry using a DuPont 2100 calorimeter at a scan rate of20° C./minute, and a spectral strength of about 5588 millilitersAbsorbance Units per gram at λ max as measured by dilution in n-butanolusing a Perking Elmer Lambda 2S UV/VIS spectrophotometer.

EXAMPLE 4 The Reaction Product of Octylphenol Ethoxylate, IsophoroneDiisocyanate and Blended Black Reactive Colorants

[0089] About 150.0 grams (0.295 equiv.) of a cyan polymeric reactivecolorant¹², about 225.0 grams (0.147 equiv.) of a violet polymericcolorant corresponding to Colorant U from Table I of U.S. Pat. No.5,231,135; about 345.0 (0.552 equiv.) of an orange polymeric reactivecolorant corresponding to Colorant B from Table I of U.S. Pat. No.5,231,135; about 450.0 grams (4.054 equiv.) of isophorone diisocyanate¹³and about 0.18 grams of dibutyltindilaurate catalyst¹⁴ were added to a3000 ml three-neck resin kettle equipped with a Trubore stirrer, a N₂atmosphere inlet, and a thermocouple-temperature controller. Thereaction mixture was heated to about 90° C. with stirring undernitrogen. After 3.5 hours at about 90° C., about 1.0 grams of additionaldibutyltindilaurate catalyst¹⁴ and about 805.0 grams (3.012 equiv.) ofoctylphenol ethoxylate¹⁵ were added and the temperature was raised toabout 130° C. and held for approximately 3.5 hours. An FT-IR of theproduct was obtained to insure that all of the isocyanate (NCO)functionality was consumed. The absence (disappearance) of a peak atabout 2285 cm⁻¹ (NCO) and the appearance (or increase in magnitude) ofpeaks at about 1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding tourethane frequencies were used to confirm this. The diurethane reactionproduct was poured into aluminum molds and allowed to cool and harden.This final colored resin product was characterized by the followingphysical properties: viscosity of about 163.0 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C., a melting pointof below ambient temperature and not measurable by electrothermalmelting pint apparatus, a T_(g) of about 3.8° C. as measured bydifferential scanning calorimetry using a DuPont 2100 calorimeter at ascan rate of 20° C./minute, and a spectral strength of about 4667milliliters Absorbance Units per gram at λ max as measured by dilutionin n-butanol using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer.

EXAMPLE 5 Cyan Ink Made From Amide Wax Polyethylene Wax, MixedUrethane/Urea Resin and Cyan Colored Urethane Resin

[0090] In a stainless steel beaker were combined about 237.5 grams ofthe cyan colored resin from Example 3, about 237.5 grams of the reactionproduct urethane/urea mixture material from Example 2 above, about 473grams of Witco S-180 stearyl stearamide¹⁶, about 50 grams ofpolyethylene wax¹⁷ and about 2 grams of Uniroyal Naugard 445antioxidant¹⁸. The materials were melted together at a temperature ofabout 125° C. in an oven, then blended by stirring in a temperaturecontrolled mantle at about 125° C. for about one hour. After stirringfor about one hour, the cyan ink was filtered through a heated Mottapparatus (available from Mott Metallurgical) using #3 Whatman filterpaper and a pressure of about 15 psi. The filtered phase change ink waspoured into molds and allowed to solidify to form ink sticks. This finalink product was characterized by the following physical properties:viscosity of about 12.7 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., a melting point of about 89° C. as measuredby differential scanning calorimetry using a DuPont 2100 calorimeter,and a T_(g) of about 21.9° C. as measured by Dynamic Mechanical Analysisusing a Rheometrics Solids Analyzer (RSAII). The spectral strength ofthe ink was determined using a spectrophotographic procedure based onthe measurement of the colorant in solution by dissolving the solid inkin butanol and measuring the absorbance using a Perkin Elmer Lambda 2SUV/VIS spectrophotometer. The spectral strength of the ink was measuredas about 1469 milliliters Absorbance Units per gram at λ max.

EXAMPLE 6

[0091] Yellow Ink Made From Amide Wax. Polyethylene Wax. MixedUrethane/Urea Resin and Yellow Colored Urethane Resin

[0092] In a stainless steel beaker were combined about 264 grams of thecolored resin from Example 1 above, about 225.7 grams of the materialfrom Example 2 above, about 458 grams of Witco S-180 stearylstearamide¹⁹, about 50 grams of polyethylene wax²⁰ and about 2.0 gramsof Uniroyal Naugard 445 antioxidant²¹. The materials were meltedtogether at a temperature of about 125° C. in an oven, then blended bystirring in a temperature controlled mantle at about 125° C. for aboutone hour. The yellow ink was then filtered through a heated Mottapparatus (available from Mott Metallurgical) using #3 Whatman filterpaper and a pressure of about 15 psi. The filtered phase change ink waspoured into molds and allowed to solidify to form ink sticks. This finalink product was characterized by the following physical properties:viscosity of about 12.7 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., a melting point of about 90° C. as measuredby differential scanning calorimetry using a DuPont 2100 calorimeter,and a T_(g) of about 20° C. as measured by Dynamic Mechanical Analysisusing a Rheometrics Solids Analyzer (RSAII). The spectral strength ofthe ink was determined using a spectrophotographic procedure based onthe measurement of the colorant in solution by dissolving the solid inkin butanol and measuring the absorbance using a Perkin Elmer Lambda 2SUV/VIS spectrophotometer. The spectral strength of the ink was measuredas about 1529 milliliters Absorbance Units per gram at λ max.

EXAMPLE 7 Black Ink Made from Amide Wax, Polyethylene Wax MixedUrethane/Urea Resin and Black Colored Urethane Resin

[0093] In a stainless steel beaker were combined about 220 grams of thecolored urethane resin from Example 4 above, about 220 grams of thereaction product urethane/urea mixture material from Example 2 above,about 508 grams of Witco S-180 stearyl stearamide²², about 50 grams ofpolyethylene wax²³ and about 2.0 grams ofUniroyal Naugard 445antioxidant²⁴. The materials were melted together at a temperature ofabout 125° C. in an oven, then blended by stirring in a temperaturecontrolled mantle at about 125° C. for about one hour. The black ink wasthen filtered through a heated Mott apparatus (available from MottMetallurgical) using #3 Whatman filter paper and a pressure of about 15psi. The filtered phase change ink was poured into molds and allowed tosolidify to form ink sticks. This final ink product was characterized bythe following physical properties: viscosity of about 12.9 cPs asmeasured by a Ferranti-Shirley cone-plate viscometer at about 140° C., amelting point of about 89° C. as measured by differential scanningcalorimetry using a DuPont 2100 calorimeter, and a T_(g) of about 16° C.as measured by Dynamic Mechanical Analysis using a Rheometrics SolidsAnalyzer (RSAII). The spectral strength of the ink was determined usinga spectrophotographic procedure based on the measurement of the colorantin solution by dissolving the solid ink in butanol and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the ink was measured as about 1434 millilitersAbsorbance Units per gram at λ max.

Print and Performance Testing

[0094] The inks in Examples 5, 6, and 7 were tested in a TektronixPhaser™ 340 printer, which uses an offset transfer printing system. Allof the above inks were found to completely transfer and to give imagesof good color, print quality and durability either as primary colors orwhen used in combination with each other or the commercially availablePhaser™ 340 printer inks.

[0095] The inks of Examples 5, 6 and 7 were poured into molded HIPSMA(High Impact Polystyrene/Maleic Anhydride) plastic cups or tubs andallowed to cool and solidify. The finished solid ink sticks from theseexamples had markedly better surface finishes and better releaseproperties from the plastic cups when compared to comparableformulations without the polyethylene wax additive.

[0096] Prints made from these examples showed better blocking resistanceat high temperatures when compared to comparable formulations withoutthe polyethylene wax additives. The blocking test used is described onpage 56 of the Proceedings of NIP12: The Twelfth International Congresson Digital Printing Technologies, published in 1996 by the Society forImaging Science and Technology.

EXAMPLE 8

[0097] About 500 grams of Petrolite PE850 wax was filtered in a Mottapparatus using Whatman #3 paper. The filtration was done at about 125°C. and 15 psi. The filtered polyethylene wax was poured into aluminumink molds and allowed to harden in the shape of Phaser™ 300 ink sticks.The wax sticks were placed in the ink reservoir of a Tektronix Phaser™300 printer. This printer was used to print a matrix of PE wax dots overthe top of images previously made using a Phaser™ 340 printer. Thematrix varied from about 1% area coverage to about 20% area coverage. Itwas found that a matrix of about 5% coverage of wax dots was a goodcompromise between placing a minimum amount of wax over the image andobtaining good document feeding performance in a photocopier. Thisoverprinting method was effective to enhance the document-feedingperformance of prints made with commercial Phaser™ 340 inks, as well asthe inks from the aforementioned U.S. patent application Ser. No.08/672,815 (now U.S. Pat. No. 5,830,942), when the output sheets werefed through the automatic document feeder of a number of different modelphotocopiers, including models made by Xerox, Canon and Minolta.

EXAMPLE 9 Cyan Ink Made From Polyethylene Wax and Compatible Amide Resin

[0098] In a stainless steel beaker were combined about 89 grams of thematerial from Example 1 of U.S. Pat. No. 5,750,604, about 170 grams ofthe material from Example 1 of U.S. application Ser. No. 09/354,237, andabout 496 grams of Polywax PE655′. The materials were melted together ata temperature of about 135° C. in an oven, then blended by stirring in atemperature controlled mantle for ½ hour at 135° C. At that time about44 grams of a cyan wax from Example 4 of U.S. Pat. No. 5,919,839 wereadded along with about 2 grams of an antioxidant²⁶ and the mixture wasstirred for an additional two hours. After the ink had mixed, 10 gramsof Hyflo Supercel filter aid (available from Fluka Chemical) was addedand stirred into the molten ink for five minutes. The ink was thenfiltered through heated (135° C.) Mott apparatus (available from MottMettalurgical) using Whatman #3 filter paper at 5 psi. The filtered inkwas poured into molds and allowed to solidify to form ink sticks. Theviscosity of the finished cyan ink was about 12.0 cPs at 135° C. asmeasured by a Rheometric Scientific RS-2000 cone-plate viscometer. Thespectral strength of about 1460 ml*A/g in butanol solution wasdetermined on a Perkin-Elmer Lambda 2S spectrophotometer. The meltingpoint of about 100° C. was measured by differential scanning calorimetryusing a DuPont 2100 calorimeter. The Tg of about 9° C. was measured bydynamic mechanical analysis using a Rheometric Scientific RSA II SolidsAnalyzer. This ink was placed in a prototype Phaser™ 840 printer whichuses an indirect printing process. The ink was printed using a printhead temperature of about 135° C. The finished prints were found to havea good color, durability and image quality.

EXAMPLE 10 Magenta Ink made from Polyethylene Wax and Compatible AmideResin

[0099] In a stainless steel beaker were combined about 93 grams of thematerial from Example 1 of U.S. Pat. No. 5,750,604, about 39 grams ofthe material from Example 4 of U.S. application Ser. No. 09/400,127,about 185 grams of the material from Example 1 of U.S. application Ser.No. 09/354,237, about 343 grams of Polywax PE655²⁷ and about 130 gramsof stearyl stearamide²⁸. In addition, 1.68 grams of an antioxidant²⁹ wasadded to the mixture. The materials were melted together at atemperature of about 135° C. in an oven, then blended by stirring in atemperature controlled mantle for ½ hour at 135° C. At that time 4.0grams of Neptun Red Base NB³⁰, 4.0 grams of Keyplast Magenta RB³¹ and2.0 grams of Bio-Soft S-100³² were added to the mixture and the mixturewas stirred for an additional two hours. After the ink had mixed, 10grams of Hyflo Supercel filter aid (available from Fluka Chemical) wasadded and stirred into the molten ink for five minutes. The ink was thenfiltered through a heated (135° C.) Mott apparatus (available from MottMettalurgical) using Whatman #3 filter paper at 5 psi. The filtered inkwas poured into molds and allowed to solidify to form ink sticks. Theviscosity of the finished cyan ink was about 11.7 cPs at 135° C. asmeasured by a Rheometric Scientific RS-2000 cone-plate viscometer. Thespectral strength of about 880 ml*A/g in butanol solution was determinedon a Perkin-Elmer Lambda 2S spectro-photometer. The melting point ofabout 103° C. was measured by differential scanning calorimetry using aDuPont 2100 calorimeter. The Tg of about 10° C. was measured by dynamicmechanical analysis using a Rheometric Scientific RSA II SolidsAnalyzer. This ink was placed in a prototype Phaserl 840 printer whichuses an indirect printing process. The ink was printed using a printhead temperature of about 135° C. The finished prints were found to havea good color, durability and image quality.

EXAMPLE 11 Yellow Ink Made From Polyethylene Wax and Compatible AmideResin

[0100] In a stainless steel beaker were combined about 94 grams of thematerial from Example 1 of U.S. Pat. No. 5,750,604, about 40 grams ofthe material from Example 4 of U.S. application Ser. No. 09/400,127,about 141 grams of the material from Example 1 of U.S. application Ser.No. 09/354,237, and about 434 grams of Polywax PE655³³. In additionabout 40 grams of stearyl stearamide³⁴ and about 2 grams of anantioxidant³⁵, were added to the mixture. The materials were meltedtogether at a temperature of about 135° C. in an oven, then blended bystirring in a temperature controlled mantle for V₂ hour at 135° C. Atthat time about 45 grams of the yellow wax from Example 1 of U.S. Pat.No. 5,919,839 and about 5 grams of a yellow dye³⁶ were added to themixture and the mixture was stirred for an additional two hours. Afterthe ink had mixed, 10 grams of Hyflo Supercel filter aid (available fromFluka Chemical) was added and stirred into the molten ink for fiveminutes. The ink was then filtered through a heated (135° C.) Mottapparatus (available from Mott Mettalurgical) using Whatman #3 filterpaper at 5 psi. The filtered ink was poured into molds and allowed tosolidify to form ink sticks. The viscosity of the finished yellow inkwas about 12.0 cPs at 135° C. as measured by a Rheometric ScientificRS-2000 cone-plate viscometer. The spectral strength of about 1304ml*A/g in butanol solution was determined on a Perkin-Elmer Lambda 2Sspectrophotometer. The melting point of about 101° C. was measured bydifferential scanning calorimetry using a DuPont 2100 calorimeter. TheTg of about 12° C. was measured by dynamic mechanical analysis using aRheometric Scientific RSA II Solids Analyzer. This ink was placed in aprototype Phaser™ 840 printer which uses an indirect printing process.The ink was printed using a print head temperature of about 135° C. Thefinished prints were found to have good color, durability and imagequality.

EXAMPLE 12 Black Ink Made From Polyethylene Wax and Compatible AmideResin

[0101] In a stainless steel beaker were combined about 78 grams of thematerial from Example 1 of U.S. Pat. No. 5,750,604, about 26 grams ofthe material from Example 4 of U.S. application Ser. No. 09/400,127,about 152 grams of the material from Example 1 of U.S. application Ser.No. 09/354,237, and about 401 grams of Polywax PE655³⁷. In additionabout 91 grams of stearyl stearamide³⁸, about 27 grams of aplasticizer³⁹ and about 2 grams of an antioxidant⁴⁰ were added to themixture. The materials were melted together at a temperature of about135° C. in an oven, then blended by stirring in a temperature controlledmantle for {fraction (1/2)} hour at 135° C. At that time 24 grams of aSavinyl Black NS⁴¹ was added to the mixture and the mixture was stirredfor an additional two hours. After the ink had mixed, 10 grams of HyfloSupercel filter aid (available from Fluka Chemical) was added andstirred into the molten ink for five minutes. The ink was then filteredthrough a heated (135° C.) Mott apparatus (available from MottMettalurgical) using Whatman #3 filter paper at 5 psi. The filtered inkwas poured into molds and allowed to solidify to form ink sticks. Theviscosity of the finished black ink was about 11.5 cPs at 135° C. asmeasured by a Rheometric Scientific RS-2000 cone-plate viscometer. Thespectral strength of about 785 ml*A/g in butanol solution was determinedin a Perkin-Elmer Lambda 2S spectrophotometer. The melting point ofabout 101° C. was measured by differential scanning calorimetry using aDuPont 2100 calorimeter. The Tg of about 7° C. was measured by dynamicmechanical analysis using a Rheometric Scientific RSA II SolidsAnalyzer. This ink was placed in a prototype Phaser™ 840 printer whichuses an indirect printing process. The ink was printed using a printhead temperature of about 135° C. The finished prints were found to havea good color, durability and image quality.

EXAMPLE 13 The Reaction Product of Hydroabietyl Alcohol and IsophoroneDiisocyanate

[0102] About 391.9 grams (1.351 moles) of Abitol E hydroabietylalcohol⁴² was added to a 1000 ml four-neck resin kettle equipped with aTrubore stirrer, an N₂ atmosphere inlet, 200 ml addition funnel, and athermocouple-temperature controller. The kettle was heated to about 100°C. with stirring under an N₂ atmosphere and about 150.0 grams (0.676moles) of isophorone diiso-cyanate⁴³ was added to the addition funnel.About 0.50 grams of dibutyltindilaurate⁴⁴ catalyst was added to theAbitol E, followed by dropwise addition of the isophorone diisocyanateover 3 hours. The temperature was gradually increased to about 155° C.during this 3 hour period. After an additional 2 hours at about 155° C.,a Fourier Transform Infrared Spectroscopy (FT-IR) of the product was runto insure all of the isocyanate (NCO) was consumed. The absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740-1680 cm⁻¹ and about1540-1530 cm⁻¹ corresponding to urethane frequencies were used toconfirm this. The final di-urethane resin product was poured intoaluminum molds and allowed to cool and harden. This final product was aclear solid resin at room temperature characterized by the followingphysical properties: viscosity of about 4,072.9 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C., a melting pointof from about 72.0° C. to about 76.0° C. as measured by anelectrothermal capillary melting point apparatus, and a T_(g) of about48° C. as measured by differential scanning calorimetry using a DuPont2100 calorimeter at a scan rate of 20° C./minute.

EXAMPLE 14 The Reaction Product of 1.5 Parts Hydroabietyl Alcohol. 0.5Parts Octadecvl Amine. and Isophorone Diisocyanate

[0103] About 240.2 grams (0.676 moles) of hydroabietyl alcohol⁴⁵ wasadded to a 1000 ml four-neck resin kettle equipped with a Truborestirrer, an N₂ atmosphere inlet, 200 ml addition funnel, and athermocouple-temperature controller. About 100.0 grams (0.45 moles) ofisophorone diisocyanate⁴⁶ was added to the addition funnel. Agitation ofthe hydroabietyl alcohol first was begun and then all of the isophoronediisocyanate was added over approximately 5 minutes. About 0.22 grams ofdibutyltindilaurate⁴⁷ catalyst was added and the reaction mixture heatedto about 125° C. under an N₂ atmosphere. After 4 hours at 125° C., about59.95 grams (0.225 moles) of octadecyl amine⁴⁸ was added and thetemperature raised to about 150° C. and held for approximately 2 hours.An FT-IR of the reaction product was run to insure all of the NCOfunctionality was consumed. The absence (disappearance) of a peak atabout 2285 cm⁻¹ (NCO) and the appearance (or increase in magnitude) ofpeaks at about 1705-1635 cm⁻¹ and about 1515-1555 cm⁻¹ corresponding tourea frequencies and about 1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹corresponding to urethane frequencies were used to confirm this. Thefinal mixed urethane/urea resin product was poured into aluminum moldsand allowed to cool and harden. This final product was a clear solidresin at room temperature characterized by the following physicalproperties: viscosity of about 314.8 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C., a melting pointof from about 67.9° C. to about 87.0° C. as measured by anelectrothermal capillary melting point apparatus, and a T_(g) of about23° C. as measured by differential scanning calorimetry using a DuPont2100 calorimeter at a scan rate of 20° C./minute.

EXAMPLE 15 The Reaction Product of 1.25 Parts Hydroabietyl Alcohol 0.75Parts Octadecvl Amine and Isophorone Diisocyanate

[0104] About 150.1 grams (0.422 moles) of hydroabietyl alcohol⁴⁹ andabout 75.0 grams (0.338 moles) of isophorone diisocyanate⁵⁰ were addedto a 500 ml three-neck resin kettle equipped with a Trubore stirrer, anN₂ atmosphere inlet, and a thermocouple-temperature controller.Agitation was begun and then about 0.22 grams of dibutyltindilaurate⁵¹catalyst was added and the reaction mixture heated to about 130° C.under an N₂ atmosphere. After 4 hours at about 130° C., about 67.45grams (0.253 moles) of octadecyl amine⁵² was added and the temperatureraised to about 150° C. and held for approximately 2 hours. An FT-IR ofthe reaction product was run to insure all of the NCO functionalityconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹(NCO)and the appearance (or increase in magnitude) of peaks at about1705-1635 cm⁻¹ and about 1515-1555 cm⁻¹ corresponding to ureafrequencies and about 1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹corresponding to urethane frequencies were used to confirm this. Thefinal mixed urethane/urea resin product was then poured into aluminummolds and allowed to cool and harden. This final product was a clearsolid resin at room temperature characterized by the following physicalproperties: viscosity of about 275.0 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C., a melting pointof from about 68.4° C. to about 89.0° C. as measured by anelectrothermal capillary melting point apparatus, and a T_(g) of about17° C. as measured by differential scanning calorimetry using a DuPont2100 calorimeter at a scan rate of 20° C./minute.

EXAMPLE 16 The Reaction Product of 1 Part Hydroabietyl Alcohol, 1 PartOctadecyl Amine and Isophorone Diisocyanate

[0105] About 120.1 grams (0.338 moles) ofhydroabietyl alcohol⁵³ andabout 75.0 grams (0.338 moles) of isophorone diisocyanate⁵⁴ was added toa 500 ml three-neck resin kettle equipped with a Trubore stirrer, an N2atmosphere inlet, and a thermocouple-temperature controller. Agitationwas begun and then about 0.22 grams of dibutyltindilaurate⁵⁵ catalystwas added and the reaction mixture heated to about 90° C. under an N₂atmosphere. After 1 hour at about 90° C. the temperature was increasedto about 110° C. and held for 2 hours. About 89.93 grams (0.338 moles)of octadecyl amine⁵⁶ was added and the temperature raised to about 130°C. and held for approximately 2 hours. An FT-IR of the reaction productwas run to insure all of the NCO functionality was consumed. The absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1705-1635 cm⁻¹ and about1515-1555 cm⁻¹ corresponding to urea frequencies and about 1740-1680cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethane frequencies wereused to confirm this. The final mixed urethane/urea resin product waspoured: into aluminum molds and allowed to cool and harden. This finalproduct was a clear solid resin at room temperature characterized by thefollowing physical properties: viscosity of about 15.7 cPs as measuredby a Ferranti-Shirley cone-plate viscometer at about 140° C., a meltingpoint of from about 73.2° C. to about 110° C. as measured by anelectrothermal capillary melting point apparatus, and a T_(g) of about16° C. as measured by differential scanning calorimetry using a DuPont2100 calorimeter at a scan rate of 20° C./minute.

[0106] While the invention has been described above with reference tospecific embodiments thereof, it is apparent that many changes,modifications and variations can be made without departing from theinventive concept disclosed herein. For example, it should be notedwhere a urethane reaction product is obtained, a single alcoholprecursor or multiple alcohol precursors may be used with an appropriateisocyanate as long as the required stoichiometric ratio is maintained.Similarly, where a urea is the reaction product, a single amineprecursor or multiple amine precursors may employed as long as therequired stoichiometric ratio is maintained. Where a urethane/ureareaction product is obtained, single or multiple alcohol and amineprecursors may be employed within the appropriate stoichiometric ratios.Accordingly, it is intended to embrace all such changes, modificationsand variations that fall within the spirit and broad scope of theappended claims.

What is claimed is:
 1. A phase change ink composition comprising: aurethane that is the reaction product of one or more alcohols and one ormore isocyanates, the alcohols comprising monohydric fused-ringalcohols; and at least one polyethylene wax.
 2. The phase change inkcomposition of claim 1 wherein the isocyanates comprise isophoronediisocyanate.
 3. The phase change ink composition of claim 1 wherein themonohydric fused-ring alcohols include one or more of hydroabietylalcohol, methyl ester of hydrogenated rosin, and decarboxylated rosin.4. The phase change ink composition of claim 1 wherein the monohydricfused-ring alcohols include one or more of hydroabietyl alcohol, methylester of hydrogenated rosin, and decarboxylated rosin; and theisocyanates comprise isophorone diisocyanate.
 5. The phase change inkcomposition of claim 1 wherein the alcohols consist of one or more ofhydroabietyl alcohol, methyl ester of hydrogenated rosin, anddecarboxylated rosin; and the isocyanates consist of isophoronediisocyanate.
 6. A phase change ink composition comprising: a urethaneresin that is the reaction product of one or more alcohols and one ormore isocyanates, the alcohols comprising fused-ring alcohols whichinclude at least three fused rings.
 7. The phase change ink compositionof claim 6 wherein the fused-ring alcohols consist of monohydricalcohols.
 8. The phase change ink composition of claim 6 wherein thefused-ring alcohols which include at least three fused rings consist ofmonohydric alcohols.
 9. The phase change ink composition of claim 6wherein the fused-ring alcohols include one or more of hydroabietylalcohol, methyl ester of hydrogenated rosin, and decarboxylated rosin.10. The phase change ink composition of claim 6 wherein the fused-ringalcohols include one or more of hydroabietyl alcohol, methyl ester ofhydrogenated rosin, and decarboxylated rosin; and the isocyanatescomprise isophorone diisocyanate.
 11. The phase change ink compositionof claim 6 wherein the alcohols consist of one or more of hydroabietylalcohol, methyl ester of hydrogenated rosin; and decarboxylated rosinand the isocyanates consist of isophorone diisocyanate.
 12. A phasechange ink composition comprising: a urethane resin that is the reactionproduct of one or more alcohols and one or more isocyanates, thealcohols comprising monohydric fused-ring alcohols having no doublebonds.
 13. The phase change ink composition of claim 12 furthercomprising a polyethylene wax.
 14. The phase change ink composition ofclaim 12 further comprising a polyethylene wax and a mono-amide.
 15. Thephase change ink composition of claim 12 wherein the monohydricfused-ring alcohols include alcohols having at least three fused rings.16. A phase change ink comprising: a urethane that is the reactionproduct of one or more alcohols and one or more isocyanates, thealcohols comprising monohydric fused-ring alcohols; at least onepolyethylene wax; and a colorant.
 17. The phase change ink of claim 16wherein the monohydric fused-ring alcohols include one or more ofhydroabietyl alcohol, methyl ester of hydrogenated rosin, anddecarboxylated rosin.
 18. The phase change ink composition of claim 16wherein the monohydric fused-ring alcohols include one or more ofhydroabietyl alcohol, methyl ester of hydrogenated rosin, anddecarboxylated rosin; and the isocyanates comprise isophoronediisocyanate.
 19. The phase change ink composition of claim 16 whereinthe alcohols consist of one or more of hydroabietyl alcohol, methylester of hydrogenated rosin, and decarboxylated rosin; and theisocyanates consist of isophorone diisocyanate.
 20. The phase change inkcomposition of claim 16 wherein the alcohols consist of one or more ofhydroabietyl alcohol, methyl ester of hydrogenated rosin, anddecarboxylated rosin; and the isocyanates consist of isophoronediisocyanate; the ink further comprising a mono-amide.
 21. A method forproducing a layer of a phase change ink on a surface of a substrate,which comprises: forming a phase change ink composition in the solidphase, the phase change ink composition comprising a phase changecarrier composition and a colorant material; said phase change carriercomposition comprising a urethane resin that is the reaction product ofat least one fused ring alcohol and an isocyanate, the fused ringalcohol including at least three fused rings; melting the ink; applyingthe melted ink to at least one surface of a substrate; and solidifyingthe applied ink on the surface of the substrate.
 22. The method of claim21 wherein the fused-ring alcohols consist of monohydric alcohols. 23.The method of claim 21 wherein the fused-ring alcohols which include atleast three fused rings consist of monohydric alcohols.
 24. The methodof claim 21 wherein the fused-ring alcohols include one or more ofhydroabietyl alcohol, methyl ester of hydrogenated rosin, anddecarboxylated rosin.
 25. The method of claim 21 wherein the fused-ringalcohols include one or more of hydroabietyl alcohol, methyl ester ofhydrogenated rosin, and decarboxylated rosin; and the isocyanatescomprise isophorone diisocyanate.
 26. The method of claim 21 wherein thealcohols consist of one or more of hydroabietyl alcohol, methyl ester ofhydrogenated rosin, and decarboxylated rosin; and the isocyanatesconsist of isophorone diisocyanate.
 27. A method of forming a phasechange ink, comprising reacting one or more alcohols with one or moreisocyanates, the alcohols comprising fused-ring alcohols which includeat least three fused rings.
 28. The method of claim 27 wherein thefused-ring alcohols consist of monohydric alcohols.
 29. The method ofclaim 27 wherein the fused-ring alcohols which include at least threefused rings consist of monohydric alcohols.
 30. The method of claim 27wherein the fused-ring alcohols include one or more of hydroabietylalcohol, methyl ester of hydrogenated rosin, and decarboxylated rosin.31. The method of claim 27 wherein the fused-ring alcohols include oneor more of hydroabietyl alcohol, methyl ester of hydrogenated rosin, anddecarboxylated rosin; and the isocyanates comprise isophoronediisocyanate.
 32. The method of claim 27 wherein the alcohols consist ofone or more of hydroabietyl alcohol, methyl ester of hydrogenated rosin,and decarboxylated rosin; and the isocyanates consist of isophoronediisocyanate.
 33. A composition comprising:

wherein R₁—R₁₉ comprise hydrogen, alkyl groups or aryl groups, and canbe the same as one another or different from one another; wherein one ormore of R₁—R₁₉ can be comprised by a ring structure; and wherein X₁comprises one or more methylene groups.
 34. The composition of claim 33wherein some of R₁—R₁₉ are methyl groups and some of R₁—R₁₉ are notmethyl groups, and wherein at least some of R₁—R₁₉ which are not methylgroups are hydrogen.
 35. A composition comprising:

wherein R₁—R₃₀ comprise hydrogen, alkyl groups or aryl groups, and canbe the same as one another or different from one another; and whereinX₁, X₂ and X₃ comprise one or more methylene groups and can be the sameas one another or different from one another.
 36. The composition ofclaim 35 wherein some of R₁—R₃₀ are methyl groups and some of R₁—R₃₀ arenot methyl groups, and wherein at least some of the R₁—R₃₀ which are notmethyl groups are hydrogen.
 37. A composition comprising:

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ comprise hydrogen, alkylgroups or aryl groups.
 38. The composition of claim 37 wherein R₁, R₂,R₃, R₄, R₅, R₆, R₇ and R₈ are methyl groups.
 39. A phase change inkcomprising:

wherein R₁—R₁₉ comprise hydrogen, alkyl groups or aryl groups, and canbe the same as one another or different from one another; wherein one ormore of R₁—R₁₉ can be comprised by a ring structure; and wherein X₁comprises one or more methylene groups.
 40. The phase change ink ofclaim 39 wherein some of R₁—R₃₀ are methyl groups and some of R₁—R₃₀ arenot methyl groups, and wherein at least some of the R₁—R₃₀ which are notmethyl groups are hydrogen.
 41. A phase change ink comprising:

wherein R₁—R₃₀ comprise hydrogen, alkyl groups-or aryl groups, and canbe the same as one another or different from one another; and whereinX₁, X₂ and X₃ comprise one or more methylene groups and can be the sameas one another or different from one another.
 42. The phase change inkof claim 41 wherein at least some of R₁—R₃₀ are methyl groups and someof R₁—R₃₀ are not methyl groups, and wherein at least some of the R₁—R₃₀which are not methyl groups are hydrogen.
 43. A phase change inkcomprising:

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ comprise hydrogen, alkylgroups or aryl groups.
 44. The phase change ink of claim 43 wherein R₁,R₂, R₃, R₄, R₅, R₆, R₇ and R₈ are methyl groups.